TW201932519A - Process for transfer imprinting - Google Patents
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- TW201932519A TW201932519A TW107145887A TW107145887A TW201932519A TW 201932519 A TW201932519 A TW 201932519A TW 107145887 A TW107145887 A TW 107145887A TW 107145887 A TW107145887 A TW 107145887A TW 201932519 A TW201932519 A TW 201932519A
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- G—PHYSICS
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- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/42—Moulds or cores; Details thereof or accessories therefor characterised by the shape of the moulding surface, e.g. ribs or grooves
- B29C33/424—Moulding surfaces provided with means for marking or patterning
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C33/00—Moulds or cores; Details thereof or accessories therefor
- B29C33/56—Coatings, e.g. enameled or galvanised; Releasing, lubricating or separating agents
- B29C33/60—Releasing, lubricating or separating agents
- B29C33/62—Releasing, lubricating or separating agents based on polymers or oligomers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- C08F112/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F112/02—Monomers containing only one unsaturated aliphatic radical
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- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
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- C08F130/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
- C08F130/02—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal containing phosphorus
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- C—CHEMISTRY; METALLURGY
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F212/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring
- C08F212/02—Monomers containing only one unsaturated aliphatic radical
- C08F212/04—Monomers containing only one unsaturated aliphatic radical containing one ring
- C08F212/06—Hydrocarbons
- C08F212/08—Styrene
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
- C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
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- C08F230/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and containing phosphorus, selenium, tellurium or a metal
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- C08F2438/00—Living radical polymerisation
- C08F2438/02—Stable Free Radical Polymerisation [SFRP]; Nitroxide Mediated Polymerisation [NMP] for, e.g. using 2,2,6,6-tetramethylpiperidine-1-oxyl [TEMPO]
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Abstract
Description
本發明係關於使用新系列的防黏層之轉移壓印法。更特別地,本發明係關於使用新系列的防黏層於奈米壓印微影製程之轉移壓印法。本發明亦係關於使用此方法得到的壓印物。This invention relates to transfer imprinting using a new series of anti-adhesive layers. More particularly, the present invention relates to transfer imprinting using a new series of anti-adhesion layers in a nanoimprint lithography process. The invention also relates to embossments obtained using this method.
奈米壓印微影術是一種製造奈米尺寸模型的方法。其為具有高產能和高解析度的簡單和低成本的奈米微影製程。其藉由將現有的圖案轉移至可聚合或可熔合之調合物的模板上而製造圖案。該可聚合的調合物基本上是在壓印製程中可藉熱或電磁射線固化的單體和/或聚合物調合物。在可熔合調合物的情況中,後者於熔化點塑形,之後冷卻。介於可聚合(或可熔合)調合物和模板(模具)之間的黏著性經控制以使能夠正確地脫模。在已知的先前技術(M. Keil等人,J. Vac. Sci. Technol. B 22(6), Nov/Dec 2004;H. Schulz等人,Proc. SPIE 3996, 244-249, 2000),另一方面,此黏著性係藉由帶有氟官能基的聚合物來控制,以確保防黏功能,並且,由於此防黏層絕對必須留在模板上,所以該聚合物亦帶有可將此防黏層接枝於模板上的官能基(通常是矽烷)。Nanoimprint lithography is a method of making nanoscale models. It is a simple and low-cost nano lithography process with high throughput and high resolution. It is patterned by transferring an existing pattern onto a template of a polymerizable or fusible blend. The polymerizable blend is essentially a monomer and/or polymer blend that can be cured by heat or electromagnetic radiation during the imprint process. In the case of a fusible blend, the latter is shaped at the point of fusion and then cooled. The adhesion between the polymerizable (or fusible) blend and the stencil (mold) is controlled to enable proper demolding. In the known prior art (M. Keil et al, J. Vac. Sci. Technol. B 22 (6), Nov/Dec 2004; H. Schulz et al, Proc. SPIE 3996, 244-249, 2000), On the other hand, this adhesion is controlled by a polymer with a fluorine functional group to ensure a release function, and since the release layer must absolutely remain on the template, the polymer also has The anti-adhesive layer is grafted to a functional group (usually decane) on the template.
轉移壓印法可以彙整成以下步驟:
模板1,圖1,係在奈米壓印情況中,以矽型材料形成。對於其他轉移壓印法,模板可為另一本質:礦物、金屬或甚至有機物。
防黏層2,圖2,係由黏著至模板但不黏著至壓印物的材料形成。
壓印物3,圖3,係由將採用經防黏層覆蓋的模板形狀之樹脂(可聚合或非可聚合調合物)形成。一旦該製程終了,自1和2的組裝品移除壓印物3 (圖4)。
適當時,在模板1和防黏層2之間添加黏著底漆。
該防黏層必須具有至少兩個性質:
防黏層必須在有或無黏著底漆的情況下黏著至模板(例如藉氧電漿活化),且其必須不黏著至壓印物。
這兩個條件難以調和,精細化學用於將這些特性結合在一起。在奈米壓印的情況中,目前的解決方案導致壓印物具有太多的重現缺陷,因而無法符合電子產品的要求。
特別地,在文獻中廣泛公開的是,提供給可聚合調合物之防黏層的表面能必須儘量低以便改良轉移品質,即,使得轉移缺陷最小化,但亦藉由避免表面污染而改良所轉移的材料的壽命(Bharat Bhushan, Springer Science & Business Media, 23 apr. 2010, page 291)。其亦必須是化學惰性、疏水性,及使模板具有良好填充性(同上),即使厚度極淺(在奈米壓印微影製程的情況中,數個奈米)亦然。此論述亦揭示於US2013/0084352和US2003/0080471中。這兩篇論文明確提到疏水性氟化合物的使用。
對模板的黏著性通常係藉矽烷作用提供,同時藉氟官能性賦予可聚合調合物防黏性質(引用文獻同上)。
WO 2012/140383提及具有與本發明中描述的方法類似的特徵的表面處理,但是該文獻沒有提到奈米壓印領域中的應用,其違背了現有技術中描述的奈米壓印方法和防黏層。Transfer imprinting can be integrated into the following steps:
Template 1, Figure 1, is formed in a stencil type in the case of nanoimprinting. For other transfer imprints, the template can be another essence: mineral, metal or even organic.
The release layer 2, Figure 2, is formed from a material that adheres to the stencil but does not adhere to the emboss.
The embossed material 3, Fig. 3, is formed of a resin (polymerizable or non-polymerizable blend) which will be formed in a template shape covered with a release layer. Once the process is complete, the embossing 3 is removed from the assembly of 1 and 2 (Fig. 4).
An adhesive primer is added between the template 1 and the release layer 2 as appropriate.
The release layer must have at least two properties:
The release layer must be adhered to the stencil with or without a primer (eg, activated by oxygen plasma) and must not adhere to the embossed material.
These two conditions are difficult to reconcile and fine chemistry is used to combine these properties. In the case of nanoimprinting, the current solution results in embossing with too many reproducible defects and thus cannot meet the requirements of electronic products.
In particular, it is widely disclosed in the literature that the surface energy of the release layer provided to the polymerizable composition must be as low as possible in order to improve the transfer quality, i.e., minimize transfer defects, but also improve the surface by avoiding surface contamination. The life of the transferred material (Bharat Bhushan, Springer Science & Business Media, 23 apr. 2010, page 291). It must also be chemically inert, hydrophobic, and provide good filling of the template (ibid.), even if the thickness is extremely shallow (in the case of nanoimprint lithography, several nanometers). This discussion is also disclosed in US 2013/0084352 and US 2003/0080471. These two papers explicitly mention the use of hydrophobic fluorine compounds.
Adhesion to the template is usually provided by the action of decane, while imparting anti-adhesive properties to the polymerizable blend by means of fluoro functionality (cited above).
WO 2012/140383 refers to surface treatments having features similar to those described in the present invention, but this document does not mention applications in the field of nanoimprinting, which are contrary to the nanoimprinting methods described in the prior art and Anti-adhesive layer.
本申請者得到與防黏層有關之普遍接受的性質相矛盾之驚人發現。
由於發明人發現一些具有高表面能量的材料完美地,甚至更佳地,執行功能,本申請人因此認為,用於可聚合或非可聚合調合物之本發明之方法的防黏層的表面能量不須儘量低。本申請人亦出示本發明之方法的防黏層不須如所述地為疏水的,尤其是藉由使用氟官能性。本申請人所發現之本發明之方法之新穎的防黏層不須藉由使用黏著底漆來製備載體。
最終,相較於使用已知防黏層,以此新穎的防黏層製造的壓印物的品質更佳,此可由在壓印上產生的缺陷量所表示。
本申請人發現之新穎的防黏層之製造更容易且更經濟。The Applicant has obtained surprising findings that contradict the generally accepted nature associated with the release layer.
Since the inventors have found that some materials with high surface energies perform perfectly, even better, performing functions, the Applicant therefore believes that the surface energy of the release layer of the method of the invention for polymerizable or non-polymerizable blends Do not have to be as low as possible. The Applicant has also shown that the release layer of the process of the invention does not have to be hydrophobic as described, especially by the use of fluoro functionality. The novel release layer of the method of the present invention found by the Applicant does not require the use of an adhesive primer to prepare the carrier.
Finally, the quality of the embossed article made with this novel release layer is better than that of the known release layer, which can be represented by the amount of defects produced on the embossing.
The novel anti-adhesion layer found by the Applicant is easier and more economical to manufacture.
本發明係關於在新穎的轉移壓印法中使用的防黏層,此防黏層包含具有至少一個共價鍵的均聚物或共聚物,當該防黏層藉熱、藉有機或無機氧化還原反應、光化學方式、藉斷裂、藉電漿、或在離子化射線的影響下而活化時,該共價鍵會生成自由基,該均聚物或共聚物具有大於5 mN/m的表面能量、於25℃或使用溫度具有大於1000 MPa的彈性模數E’、和具有大於500 g/mol的重量平均分子量。The present invention relates to a release layer for use in a novel transfer embossing process comprising a homopolymer or copolymer having at least one covalent bond, when the release layer is oxidized by organic or inorganic The covalent bond generates a free radical when the reduction reaction, photochemical means, by cleavage, by plasma, or activation under the influence of ionizing radiation, the homopolymer or copolymer having a surface greater than 5 mN/m The energy has an elastic modulus E' greater than 1000 MPa at 25 ° C or a use temperature, and a weight average molecular weight greater than 500 g/mol.
本發明之方法中作為防黏層的均聚物或共聚物可藉任何途徑得到,其中可提及的是聚縮合反應、開環聚合反應、或陰離子、陽離子或自由基聚合反應,後者可以是經控制或未經控制的。當共聚物係製自自由基聚合反應或短鏈聚合反應時,此可藉任何已知技術控制,如,NMP (氮氧化物中介的聚合反應)、RAFT (可逆性加成和裂鏈轉移)、ATRP (原子轉移自由基聚合反應)、INIFERTER (引發劑-轉移-終止反應)、RITP (可逆性碘轉移聚合反應)或ITP (碘轉移聚合反應)。The homopolymer or copolymer as the anti-adhesion layer in the method of the present invention can be obtained by any route, and a polycondensation reaction, a ring-opening polymerization reaction, or an anionic, cationic or radical polymerization reaction can be mentioned, and the latter can be Controlled or uncontrolled. When the copolymer is prepared from a free radical polymerization or a short chain polymerization, this can be controlled by any known technique, such as NMP (nitrogen oxide-mediated polymerization), RAFT (reversible addition and split chain transfer). , ATRP (Atom Transfer Radical Polymerization), INIFERTER (Initiator-Transfer-Termination Reaction), RITP (Reversible Iodine Transfer Polymerization) or ITP (Iodine Transfer Polymerization).
較佳的是未包含金屬的聚合法。較佳地,該共聚物係藉自由基聚合反應製備,且更特別是藉受控的自由基聚合反應製備,又更特別的是藉氮氧化物中介的聚合反應製備。A polymerization method which does not contain a metal is preferred. Preferably, the copolymer is prepared by free radical polymerization, and more particularly by controlled free radical polymerization, and more particularly by polymerization mediated by nitrogen oxides.
本發明的上下文中使用的均聚物或共聚物可為非晶狀、晶狀或半晶狀、或熱固性的。The homopolymer or copolymer used in the context of the present invention may be amorphous, crystalline or semicrystalline, or thermoset.
本發明的上下文中使用的均聚物或共聚物對應於通式:R1 A R2
其中
A是生成自由基的共價鍵,其於25℃的鍵能是介於90和270 kJ/mol之間,且較佳介於100和170 kJ/mol之間,根據Kerr, Chem. Rev. 66, 465-500(1966)描述的方法測定。The homopolymer or copolymer used in the context of the present invention corresponds to the formula: R1 A R2
among them
A is a free radical generating covalent bond having a bond energy between 25 and 270 kJ/mol at 25 ° C, and preferably between 100 and 170 kJ/mol, according to Kerr, Chem. Rev. 66 , 465-500 (1966) method determination.
較佳地,其為碳-氧鍵,例如於烷氧基胺中者。
更特別地,較佳者是自安定的自由基(1)衍生的烷氧基胺:
其中基團RL
具有大於15.0342 g/mol的莫耳質量。基團RL
可為鹵素原子(如氯、溴或碘)、飽和或未飽和的直鏈或環狀烴基團(如,烷基或苯基)、或酯基-COOR或烷氧基-OR或膦酸基-PO(OR)2
,只要其具有大於15.0342的莫耳質量即可。單價基團RL
是指在相對於氮氧化物基團的β位置。式(1)中的碳原子和氮原子的剩餘價數可以鍵結至各種基團,如氫原子或烴系基團,例如烷基、芳基或芳烷基,包含1至10個碳原子。不排除式(1)中的碳原子和氮原子經由二價基團連接在一起,以形成環。較佳地,但是,式(1)中的碳原子和氮原子的剩餘價數鍵結至單價基團。較佳地,基團RL
具有超過30 g/mol的莫耳質量。基團RL
可以,例如,具有介於40和450 g/mol之間的莫耳質量。例如,基團RL
可為包含磷醯基的基團,該基團RL
可以式(2)表示:
其中R1
和R2
,其可相同或不同,可選自烷基、環烷基、烷氧基、芳氧基、芳基、芳烷氧基、全氟烷基和芳烷基,且可包含1至20個碳原子。R1
和/或R2
亦可為鹵素原子,如,氯、溴、氟或碘原子。基團RL
亦可包含至少一個芳環,如,苯基或萘基,該環可經取代,例如經包含1至4個碳原子的烷基取代。Preferably, it is a carbon-oxygen bond, such as in an alkoxyamine.
More particularly, alkoxyamines derived from the stable free radical (1) are preferred:
Wherein the group R L has a molar mass greater than 15.0342 g/mol. The group R L may be a halogen atom (such as chlorine, bromine or iodine), a saturated or unsaturated linear or cyclic hydrocarbon group (eg alkyl or phenyl), or an ester group -COOR or alkoxy-OR Or phosphonate-PO(OR) 2 as long as it has a molar mass greater than 15.0342. The monovalent group R L refers to the β position relative to the nitrogen oxide group. The remaining valence of the carbon atom and the nitrogen atom in the formula (1) may be bonded to various groups such as a hydrogen atom or a hydrocarbon group such as an alkyl group, an aryl group or an aralkyl group, and contains 1 to 10 carbon atoms. . It is not excluded that the carbon atom and the nitrogen atom in the formula (1) are linked together via a divalent group to form a ring. Preferably, however, the remaining valence of the carbon and nitrogen atoms in formula (1) is bonded to a monovalent group. Preferably, the group R L has a molar mass of more than 30 g/mol. The group R L can, for example, have a molar mass of between 40 and 450 g/mol. For example, the group R L may be a group containing a phosphonium group, and the group R L may be represented by the formula (2):
Wherein R 1 and R 2 , which may be the same or different, may be selected from the group consisting of alkyl, cycloalkyl, alkoxy, aryloxy, aryl, aralkoxy, perfluoroalkyl and aralkyl, and may be Contains 1 to 20 carbon atoms. R 1 and/or R 2 may also be a halogen atom such as a chlorine, bromine, fluorine or iodine atom. The group R L may also comprise at least one aromatic ring, such as a phenyl or naphthyl group, which may be substituted, for example by an alkyl group containing from 1 to 4 carbon atoms.
更特別地,較佳者為衍生自下列安定基團的烷氧基胺:
- N-(三級丁基)-1-苯基-2-甲基丙基氮氧化物、
- N-(三級丁基)-1-(2-萘基)-2-甲基丙基氮氧化物、
- N-(三級丁基)-1-二乙基膦醯基-2,2-二甲基丙基氮氧化物、
- N-(三級丁基)-1-二苄基膦醯基-2,2-二甲基丙基氮氧化物、
- N-苯基-1-二乙基膦醯基-2,2-二甲基丙基氮氧化物、
- N-苯基-1-二乙基膦醯基-1-甲基乙基氮氧化物、
- N-(1-苯基-2-甲基丙基)-1-二乙基膦醯基-1-甲基乙基氮氧化物、
- 4-酮基-2,2,6,6-四甲基-1-哌啶氧基、
- 2,4,6-三-三級丁基苯氧基氮氧化物。More particularly, alkoxyamines derived from the following stabilizing groups are preferred:
- N-(tributyl)-1-phenyl-2-methylpropyl oxynitride,
- N-(tributyl)-1-(2-naphthyl)-2-methylpropyl oxynitride,
- N-(tributyl)-1-diethylphosphonium-2,2-dimethylpropyl oxynitride,
- N-(tributyl)-1-dibenzylphosphino-based-2,2-dimethylpropyl oxynitride,
- N-phenyl-1-diethylphosphonium-2,2-dimethylpropyl oxynitride,
- N-phenyl-1-diethylphosphonium-1-methylethyl oxynitride,
- N-(1-phenyl-2-methylpropyl)-1-diethylphosphonium-1-methylethyl oxynitride,
- 4-keto-2,2,6,6-tetramethyl-1-piperidinyloxy,
- 2,4,6-tris-tert-butylphenoxy oxynitride.
除了其鍵能以外,受控的自由基聚合反應中使用的烷氧基胺必須能夠良好地控制單體的鏈結。因此,它們並非都能很好地控制某些單體。例如,自TEMPO衍生的烷氧基胺只能控制有限數量的單體;自2,2,5-三甲基-4-苯基-3-氮雜己烷-3-氮氧化物(TIPNO)衍生的烷氧基胺亦然。另一方面,對應於式(1)之其他氮氧化物系烷氧基胺,特別是自對應於式(2)的氮氧化物衍生者,更特別是自N-三級丁基-1-二乙基膦醯基-2,2-二甲基丙基氮氧化物衍生者,使得可以擴展到大量單體於這些單體的受控自由基聚合反應。
此外,烷氧基胺引發(opening)溫度亦影響了經濟因素。使用低溫將為較佳,以使得工業難度最小化。自對應於式(1)的氮氧化物衍生的烷氧基胺,特別是自對應於式(2)的氮氧化物衍生者,更特別是自N-三級丁基-1-二乙基膦醯基-2,2-二甲基丙基氮氧化物衍生者,因此自TEMPO或2,2,5-三甲基-4-苯基-3-氮雜己烷-3-氮氧化物(TIPNO)衍生者將為較佳。In addition to its bond energy, the alkoxyamine used in the controlled free radical polymerization must be able to control the chain of the monomer well. Therefore, they do not all have good control over certain monomers. For example, alkoxyamines derived from TEMPO can only control a limited number of monomers; from 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitrogen oxide (TIPNO) The same is true for the derived alkoxyamines. On the other hand, other nitrogen oxide-based alkoxyamines corresponding to the formula (1), particularly from the nitrogen oxide derivative corresponding to the formula (2), more particularly from N-tertiary butyl-1- The diethylphosphonium-2,2-dimethylpropyl oxynitride derivative allows for the extended free radical polymerization of a large number of monomers to these monomers.
In addition, the alkoxyamine opening temperature also affects economic factors. It would be better to use low temperatures to minimize industrial difficulty. Alkoxyamine derived from a nitrogen oxide corresponding to formula (1), especially from a nitrogen oxide derivative corresponding to formula (2), more particularly from N-tertiary butyl-1-diethyl Derivative of phosphinyl-2,2-dimethylpropyl oxynitride, thus from TEMPO or 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitrogen oxide (TIPNO) derivatives will be preferred.
R1是均聚物或共聚物和R2是任何類型的斷片:聚合物、共聚物或二者皆非。較佳地,R2是自受控或非受控的自由基聚合反應引發劑的分解反應得到的斷片。R1 is a homopolymer or copolymer and R2 is a fragment of any type: polymer, copolymer or both. Preferably, R2 is a fragment obtained from the decomposition reaction of a controlled or uncontrolled free radical polymerization initiator.
更佳地,R1代表均聚物、無規或嵌段、遞變或梳形共聚物,其藉SEC測定的分子量為大於500 g/mol,和R2是具有重量<1000 g/mol的分子基團。More preferably, R1 represents a homopolymer, random or block, tapered or comb copolymer having a molecular weight greater than 500 g/mol as determined by SEC, and R2 being a molecular weight having a weight of <1000 g/mol group.
遞變共聚物是指至少兩種單體之共聚物,通常藉活性或擬活性(living or pseudo-living)聚合反應得到。憑藉這些聚合方法,聚合物鏈同時生長並因此在每個時刻加入相同比例的共聚單體。共聚單體在聚合物鏈中的分佈因此取決於合成期間內共聚單體的相對濃度的改變。關於遞變共聚物的理論描述,將參考以下文獻:T. Pakula & al., Macromol. Theory Simul. 5, 987-1006(1996);A. Aksimetiev & al. J. of Chem. Physics 111, no. 5;M. Janco J. Polym. Sci., Part A:Polym. Chem.(2000), 38(15), 2767-2778;M. Zaremski & al, Macromolecules(2000), 33(12), 4365-4372;K. Matyjaszewski & al. J. Phys. Org. Chem.(2000), 13(12), 775-786;Gray Polym. Prepr.(Am. Chem. Soc., Div. Polym. Chem.)(2001), 42(2), 337-338;K. Matyjaszewski Chem. Rev.(Washington, D. C.)(2001), 101(9), 2921-2990。A tapered copolymer refers to a copolymer of at least two monomers, usually obtained by living or pseudo-living polymerization. By virtue of these polymerization methods, the polymer chains grow simultaneously and thus the same proportion of comonomer is added at each moment. The distribution of comonomers in the polymer chain therefore depends on the change in the relative concentration of comonomers during the synthesis. For a theoretical description of tapered copolymers, reference will be made to the following documents: T. Pakula & al., Macromol. Theory Simul. 5, 987-1006 (1996); A. Aksimetiev & al. J. of Chem. Physics 111, no 5;M. Janco J. Polym. Sci., Part A: Polym. Chem. (2000), 38(15), 2767-2778; M. Zaremski & al, Macromolecules (2000), 33(12), 4365 -4372; K. Matyjaszewski & al. J. Phys. Org. Chem. (2000), 13(12), 775-786; Gray Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.) (2001), 42(2), 337-338; K. Matyjaszewski Chem. Rev. (Washington, DC) (2001), 101(9), 2921-2990.
關於可用於R1的單體,可提到的是:
用於藉聚縮合反應的聚合物和共聚物之先質:用於製備下列的單體:聚醯胺或共聚醯胺、聚酯或共聚酯、聚酯醯胺或共聚酯醯胺、聚醚、聚醯亞胺、聚酮、聚醚酮,單獨或混合物。
用於藉陰離子或陽離子聚合反應或開環聚合反應之聚合物和共聚物的先質:乙烯基、乙烯基芳族、亞乙烯基、二烯、烯烴系、烯丙基或(甲基)丙烯酸系單體、內酯類、碳酸酯類、內醯胺類、丙交酯類或乙交酯類、噁唑啉類、環氧化物類、環矽氧烷類,單獨或混合物。
用於藉自由基聚合反應之聚合物和共聚物之先質:
至少一個乙烯基、亞乙烯基、二烯、烯烴系、烯丙基或(甲基)丙烯酸系單體。此單體更特別地選自:乙烯基芳族單體,如,苯乙烯或經取代的苯乙烯,尤其是α-甲基苯乙烯、單氟、二氟、三氟、四氟或五氟苯乙烯;丙烯酸系單體(如,丙烯酸或其鹽);丙烯酸烷酯、丙烯酸環烷酯或芳酯(如,丙烯酸甲酯、乙酯、丁酯、乙基己酯或苯酯);丙烯酸羥烷酯(如,丙烯酸2-羥基乙酯);丙烯酸醚烷酯(如,丙烯酸2-甲氧基乙酯);烷氧基-或芳氧基-聚烷二醇丙烯酸酯(如,甲氧基聚乙二醇丙烯酸酯、乙氧基聚乙二醇丙烯酸酯、甲氧基聚丙二醇丙烯酸酯、甲氧基聚乙二醇-聚丙二醇丙烯酸酯)、或其混合物;丙烯酸胺基烷酯(如,丙烯酸2-(二甲基胺基)乙酯(DMAEA);含氟的丙烯酸酯;含矽基的丙烯酸酯;含磷的丙烯酸酯(如,烷二醇磷酸酯丙烯酸酯);丙烯酸環氧丙酯或丙烯酸二環戊烯氧基乙;甲基丙烯酸系單體(如,甲基丙烯酸酯或其鹽);甲基丙烯酸烷酯、環烷酯、烯酯或芳酯(如,甲基丙烯酸甲酯(MMA)、甲基丙基酸月桂酯、甲基丙烯酸環己酯、甲基丙烯酸烯丙酯、甲基丙烯酸酯苯酯或甲基丙烯酸萘酯);甲基丙烯酸羥烷酯(如,甲基丙烯酸2-羥基乙酯或甲基丙烯酸2-羥基丙酯);甲基丙烯酸醚烷酯(如,甲基丙烯酸2-乙氧基乙酯);烷氧基-或芳氧基-聚烷二醇甲基丙烯酸酯(如,甲氧基聚乙二醇甲基丙烯酸酯、乙氧基乙二醇甲基丙烯酸酯、甲氧基丙二醇甲基丙烯酸酯、甲氧基聚乙二醇-聚丙二醇甲基丙烯酸酯)、或其混合物;甲基丙烯酸胺基烷酯(如,甲基丙烯酸2-(二甲基胺基)酯(DMAEMA));含氟的甲基丙烯酸酯(如,甲基丙烯酸2,2,2-三氟乙酯);含矽基的甲基丙烯酸酯(如,3-甲基丙烯醯基丙基三甲基矽烷);含磷的甲基丙烯酸酯(如,烷二醇磷酸酯甲基丙烯酸酯);羥乙基咪唑啶酮甲基丙烯酸酯、羥乙基咪唑啶酮甲基丙烯酸酯、甲基丙烯酸2-(2-酮基-1-咪唑啶基)乙酯;丙烯腈;丙烯醯胺或經取代的丙烯醯胺;4-丙烯醯嗎啉;N-羥甲基丙烯醯胺;甲基丙烯醯胺或經取代的甲基丙烯醯胺;N-羥甲基甲基丙烯醯胺;甲基丙烯醯胺基丙基三甲基氯化銨(MAPTAC);甲基丙烯酸環氧丙酯;甲基丙烯酸二環戊烯氧基乙酯;衣康酸;馬來酸或其鹽;馬來酸酐;烷基或烷氧基-或芳氧基-聚烷二醇馬來酸酯或半甲基丙烯酸酯;乙烯基吡啶;乙烯基吡咯啶酮、(烷氧基)聚(烷二醇)乙烯醚或二乙烯醚(如,甲氧基聚(乙二醇)乙烯醚、聚(乙二醇)二乙烯醚;烯烴系單體,其中可提到的是乙烯、丁烯、己烯和1-辛烯、二烯單體(包括丁二烯、異戊二烯)和含氟的烯烴系單體、和亞乙烯基單體,其中可提到的是偏二氟乙烯,單獨或至少二種上述單體之混合物。Regarding the monomers that can be used for R1, mention may be made of:
Precursor for polymers and copolymers used in polycondensation reactions: for the preparation of the following monomers: polydecylamine or copolyamine, polyester or copolyester, polyester decylamine or copolyester decylamine, Polyether, polyimine, polyketone, polyether ketone, alone or in combination.
Precursors for polymers and copolymers by anionic or cationic or ring-opening polymerization: vinyl, vinyl aromatic, vinylidene, diene, olefin, allyl or (meth)acrylic acid Monomers, lactones, carbonates, decylamines, lactides or glycolides, oxazolines, epoxides, cyclopentanes, alone or in mixtures.
Precursors for polymers and copolymers used in free radical polymerization:
At least one vinyl, vinylidene, diene, olefin, allyl or (meth)acrylic monomer. The monomer is more particularly selected from the group consisting of vinyl aromatic monomers such as styrene or substituted styrenes, especially alpha-methylstyrene, monofluoro, difluoro, trifluoro, tetrafluoro or pentafluoro. Styrene; acrylic monomer (eg, acrylic acid or a salt thereof); alkyl acrylate, cycloalkyl acrylate or aryl ester (eg, methyl acrylate, ethyl acrylate, butyl acrylate, ethyl hexyl or phenyl ester); acrylic acid a hydroxyalkyl ester (eg, 2-hydroxyethyl acrylate); an alkyl acrylate (eg, 2-methoxyethyl acrylate); an alkoxy- or aryloxy-polyalkylene glycol acrylate (eg, A Oxypolyethylene glycol acrylate, ethoxypolyethylene glycol acrylate, methoxypolypropylene glycol acrylate, methoxy polyethylene glycol-polypropylene glycol acrylate), or a mixture thereof; aminoalkyl acrylate (eg, 2-(dimethylamino)ethyl acrylate (DMAEA); fluorine-containing acrylate; thiol-containing acrylate; phosphorus-containing acrylate (eg, alkyl glycol phosphate acrylate); acrylic acid Glycidyl acrylate or dicyclopentenyloxyethyl acrylate; methacrylic monomer (eg, methacrylate or a salt thereof); alkyl methacrylate , cycloalkyl ester, enester or aryl ester (eg, methyl methacrylate (MMA), methyl propyl laurate, cyclohexyl methacrylate, allyl methacrylate, phenyl methacrylate Or naphthyl methacrylate); hydroxyalkyl methacrylate (eg 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate); ether alkyl methacrylate (eg, methacrylic acid 2- Ethoxyethyl ester); alkoxy- or aryloxy-polyalkylene glycol methacrylate (eg, methoxy polyethylene glycol methacrylate, ethoxyethylene glycol methacrylate, Methoxypropylene glycol methacrylate, methoxy polyethylene glycol-polypropylene glycol methacrylate), or a mixture thereof; aminoalkyl methacrylate (eg, 2-(dimethylamino) methacrylate ) ester (DMAEMA)); fluorine-containing methacrylate (eg, 2,2,2-trifluoroethyl methacrylate); thiol-containing methacrylate (eg, 3-methylpropenyl) Propyl trimethyl decane); phosphorus-containing methacrylate (eg, alkyl glycol phosphate methacrylate); hydroxyethyl imidazolidinone methacrylate, hydroxyethyl imidazolidinone methyl propyl Ethyl ester, 2-(2-keto-1-imidazolidinyl)ethyl methacrylate; acrylonitrile; acrylamide or substituted acrylamide; 4-propenylmorpholine; N-hydroxymethyl Acrylamide; methacrylamide or substituted methacrylamide; N-methylol methacrylamide; methacrylamidopropyltrimethylammonium chloride (MAPTAC); methyl Glycidyl acrylate; dicyclopentenyloxyethyl methacrylate; itaconic acid; maleic acid or a salt thereof; maleic anhydride; alkyl or alkoxy- or aryloxy-polyalkylene glycol horse Ethyl ester or hemimethacrylate; vinyl pyridine; vinyl pyrrolidone, (alkoxy) poly(alkylene glycol) vinyl ether or divinyl ether (eg, methoxy poly(ethylene glycol) ethylene Ether, poly(ethylene glycol) divinyl ether; olefinic monomers, among which are ethylene, butene, hexene and 1-octene, diene monomers (including butadiene, isoprene) And a fluorine-containing olefin-based monomer, and a vinylidene monomer, among which vinylidene fluoride, alone or a mixture of at least two of the above monomers may be mentioned.
較佳地,R1是均聚、共聚、寡聚或共寡聚基團,和R2是硝氧基。Preferably, R1 is a homopolymeric, copolymeric, oligomeric or co-oligomeric group, and R2 is a nitroxyl group.
較佳地,R2是N-(三級丁基)-1-二乙基膦醯基-2,2-二甲基丙基氮氧化物。Preferably, R2 is N-(tert-butyl)-1-diethylphosphonium-2,2-dimethylpropyl oxynitride.
較佳地,R1是無規共聚物或均聚物,藉SEC使用聚苯乙烯標準物測定,其數量平均分子量是介於500和200000 g/mol之間,更佳介於1000和20000 g/mol之間,且又更佳介於5000和10000 g/mol之間,如此以根據本發明之方法得到具有低於50 nm,較佳低於20 nm,更佳低於10 nm且更尤其低於5 nm之均聚物或共聚物的澱積物。R1的分散性(重量平均分子量對數量平均分子量的比)是低於5,更特別低於2,且較佳低於1.5。Preferably, R1 is a random copolymer or homopolymer, determined by SEC using polystyrene standards, and having a number average molecular weight of between 500 and 200,000 g/mol, more preferably between 1,000 and 20,000 g/mol. Between 5,000 and 10000 g/mol, and more preferably between 50 and 190 g, preferably less than 20 nm, more preferably less than 10 nm and more particularly less than 5, according to the method of the invention. A deposit of a homopolymer or copolymer of nm. The dispersibility of R1 (ratio of weight average molecular weight to number average molecular weight) is less than 5, more particularly less than 2, and preferably less than 1.5.
較佳地,R1由單體形成,其中可提及的是苯乙烯、甲基丙烯酸甲酯、甲基丙烯酸環氧丙酯(GMA)、甲基丙烯酸2-羥基乙酯(HEMA)、丙烯酸甲酯或乙酯、含氟的丙烯酸酯或甲基丙烯酸酯、和單氟、二氟、三氟、四氟或五氟苯乙烯。苯乙烯存在於該共聚物中的莫耳量範圍較佳是由40至100%且更佳由60至100%。Preferably, R1 is formed of a monomer, and styrene, methyl methacrylate, glycidyl methacrylate (GMA), 2-hydroxyethyl methacrylate (HEMA), acrylic acid may be mentioned. Ester or ethyl ester, fluorine-containing acrylate or methacrylate, and monofluoro, difluoro, trifluoro, tetrafluoro or pentafluorostyrene. The molar amount of styrene present in the copolymer preferably ranges from 40 to 100% and more preferably from 60 to 100%.
根據本發明之第一較佳形式,本發明之無規共聚物係以2-甲基-2-[N-三級丁基-N-(二乙氧基磷醯基-2,2-二甲基丙基)胺氧基]丙酸和苯乙烯製得。According to a first preferred form of the invention, the random copolymer of the invention is 2-methyl-2-[N-tertiary butyl-N-(diethoxyphosphonyl-2,2-di Methylpropyl)aminooxy]propionic acid and styrene are prepared.
根據本發明之第二較佳形式,本發明之無規共聚物係先使2-甲基-2-[N-三級丁基-N-(二乙氧基磷醯基-2,2-二甲基丙基)胺氧基]丙酸與官能性單體(選自甲基丙烯酸環氧丙酯(GMA)或甲基丙烯酸2-羥基乙酯(HEMA),和較佳地丙烯酸環氧丙酯(GA)或丙烯酸2-羥基乙酯(HEA))反應,使得添加單一種單體單元,之後此反應的產物用作為一或多種非官能性單體(如,(甲基)丙烯酸烷酯)或苯乙烯單體(較佳僅苯乙烯)的引發劑。因此,在本發明的此較佳形式中,本發明之共聚物是2-甲基-2-[N-三級丁基-N-(二乙氧基磷醯基-2,2-二甲基丙基)胺氧基]丙酸與丙烯酸羥乙酯和苯乙烯的合成產物。According to a second preferred form of the invention, the random copolymer of the invention is first made 2-methyl-2-[N-tertiary butyl-N-(diethoxyphosphonyl-2,2- Dimethylpropyl)aminooxy]propionic acid and a functional monomer selected from the group consisting of glycidyl methacrylate (GMA) or 2-hydroxyethyl methacrylate (HEMA), and preferably acrylic acrylate The propyl ester (GA) or 2-hydroxyethyl acrylate (HEA) is reacted such that a single monomer unit is added, after which the product of the reaction is used as one or more non-functional monomers (eg, (meth) acrylate An initiator of an ester) or styrene monomer, preferably only styrene. Thus, in this preferred form of the invention, the copolymer of the invention is 2-methyl-2-[N-tertiary butyl-N-(diethoxyphosphonyl-2,2-dimethyl Synthesis of propyl)aminooxy]propionic acid with hydroxyethyl acrylate and styrene.
關於在轉移壓印法中用作為防黏層之均聚物或共聚物的表面能量,其高於5 mN/m,較佳高於25 mN/m,且較佳高於40 mN/m,此係藉懸滴法(pendant drop method)以OWRK數學處理測得。Regarding the surface energy of the homopolymer or copolymer used as the anti-adhesion layer in the transfer imprinting method, it is higher than 5 mN/m, preferably higher than 25 mN/m, and preferably higher than 40 mN/m, This was measured by OWRK mathematical processing by a pendant drop method.
關於在轉移壓印法中用作為防黏層之均聚物或共聚物的彈性模數E’,其於25℃或使用溫度,為大於1000 MPa,此係藉DMA(動態機械分析)測得。Regarding the elastic modulus E' used as a homopolymer or copolymer of the anti-adhesive layer in the transfer imprint method, which is greater than 1000 MPa at 25 ° C or the use temperature, which is measured by DMA (Dynamic Mechanical Analysis) .
在非晶狀聚合物的情況中,將僅可能考慮均聚物或共聚物的Tg,且其將高於25℃或使用溫度,此係藉DMA測得。In the case of amorphous polymers, it will only be possible to consider the Tg of the homopolymer or copolymer, and it will be above 25 ° C or the temperature of use, as measured by DMA.
此外,介於形成壓印物之防黏共聚物或均聚物和澱積的樹脂之間的Flory-Huggins chi參數必須為正值。In addition, the Flory-Huggins chi parameter between the anti-adhesive copolymer or homopolymer forming the imprint and the deposited resin must be positive.
關於使用防黏層(其為本發明之標的)之轉移壓印法,其特徵在於以下步驟:
- 將防黏層澱積在模板上,該模板事先未經處理或經黏著底漆(表面活化電漿)處理,此防黏層包含具有至少一個共價鍵的均聚物或共聚物,當分子藉熱、藉有機或無機氧化還原反應、光化學方式、藉斷裂、藉電漿、或在離子化射線的影響下而活化時,該共價鍵會生成自由基,該均聚物或共聚物具有大於5 mN/m的表面能量、於25℃或使用溫度具有大於1000 MPa的彈性模數E’,
- 藉熱、藉有機或無機氧化還原反應、光化學方式、藉斷裂、藉電漿、或在離子化射線的影響下活化該共價鍵以生成自由基,以在該模板上形成具有低於50 nm,較佳低於20 nm,更佳低於10 nm,特佳低於5 nm的厚度的膜,
- 澱積或積層厚度範圍由100 nm至5 mm的聚合物樹脂,無論是否事先澱積在具有大於1 GPa的楊氏模數之載體上,
- 聚合或冷卻作為壓印物的該樹脂,
- 移除該壓印物。A transfer imprint method using an anti-adhesion layer which is the subject of the present invention is characterized by the following steps:
- depositing an anti-adhesive layer on the stencil which has been previously untreated or treated with an adhesive primer (surface activated plasma) comprising a homopolymer or copolymer having at least one covalent bond When the molecule is activated by heat, by organic or inorganic redox reaction, photochemically, by fragmentation, by plasma, or under the influence of ionizing radiation, the covalent bond generates a radical, the homopolymer or copolymerization The material has a surface energy greater than 5 mN/m, and has an elastic modulus E' greater than 1000 MPa at 25 ° C or a use temperature.
- by means of heat, by organic or inorganic redox reaction, photochemically, by fragmentation, by plasma, or by activation of the covalent bond under the influence of ionizing radiation to generate free radicals to form below the template a film having a thickness of 50 nm, preferably less than 20 nm, more preferably less than 10 nm, particularly preferably less than 5 nm,
- deposition or lamination of a polymer resin having a thickness ranging from 100 nm to 5 mm, whether or not previously deposited on a carrier having a Young's modulus greater than 1 GPa,
- polymerizing or cooling the resin as an imprint,
- Remove the embossed material.
該防黏層(其為本發明之標的)可用於任何類型的轉移壓印法(製造壓印物),該轉移壓印法可為用於微影術的巨壓印(macroimprinting)、微壓印(microimprinting)、奈米壓印(nanoimprinting)或模衝壓印(stampling)、微電子組件、光子組件、光電子應用(LED、光伏打裝置)、MEMS、NEMS、記憶體、微流體、生物技術、生物醫藥、自清潔表面、抗反射表面、顯示器(螢幕)、用於複製載體(產生壓印物)、音頻或視頻(如,CD或DVD)、或乙烯磁碟的轉移壓印、或更巨觀的物件(如,用於休閒、運動、或汽車或航空領域的技術應用之物件)。The release layer, which is the subject of the present invention, can be used in any type of transfer imprinting process (manufacturing of imprints), which can be macroimprinting, micro-pressure for lithography. Microimprinting, nanoimprinting or stamping, microelectronic components, photonic components, optoelectronic applications (LEDs, photovoltaic devices), MEMS, NEMS, memory, microfluidics, biotechnology, Biomedicine, self-cleaning surfaces, anti-reflective surfaces, displays (screens), transfer embossing for reproduction of carriers (for embossing), audio or video (eg CD or DVD), or vinyl disk, or larger Objects (eg, objects used in leisure, sports, or technical applications in the automotive or aerospace industry).
較佳地,該防黏層(其為本發明之標的)可用於奈米壓印微影製程(nanoimprint lithography processes)。Preferably, the release layer, which is the subject of the present invention, can be used in nanoimprint lithography processes.
取決於轉移壓印法的類型,模板的本質可為半導體、金屬、陶瓷、有機玻璃,包括旋塗於玻璃上(spin-on-glass)和旋塗於碳上(spin-on-carbon)類型的材料。Depending on the type of transfer embossing, the nature of the template can be semiconductor, metal, ceramic, plexiglass, including spin-on-glass and spin-on-carbon types. s material.
實例1
此實例中,製得根據本發明之防黏層(下文中稱為ASL2-本發明):
•自Arkema銷售的市售烷氧基胺BlocBuilder®
MA製備羥基官能化的烷氧基胺(AM-OH,引發劑)
將下列引入至經氮氣沖刷脫氣的1升圓底燒瓶中:
-226.17 g的BlocBuilder®
MA(1莫耳當量)
-68.9 g的丙烯酸2-羥基乙酯(1莫耳當量)
-548 g的異丙醇。
此反應混合物回流(80℃) 4小時及之後在真空下蒸除異丙醇。得到297 g的羥基官能化的烷氧基胺(AM-OH引發劑),呈非常黏稠的黃色油形式。
•官能化的聚苯乙烯之製備
260.89 g的甲苯、及600 g的苯乙烯和20.89 g的AM-OH引發劑引至配備機械攪拌器和護套的不銹鋼反應器中。
攪拌反應混合物並藉由在室溫下通入氮氣而脫氣30分鐘。
之後使得反應介質的設定溫度為115℃(材料溫度是108℃)。在整個聚合反應中維持溫度於115℃,直到單體的轉化率達到50%。於固定間隔取得樣品,以藉重量分析(測定無水萃出物)定出聚合反應動力學。
達到50%轉化率時,反應介質冷卻至60℃,並在真空下蒸除溶劑和殘餘單體。蒸發之後,以製得約25質量%的聚合物溶液之量將甲基乙基酮加至反應介質中。
之後將此聚合物溶液逐滴引至含有非溶劑(庚烷)的燒杯中,以造成聚合物沉澱。溶劑和非溶劑(甲基乙基酮/庚烷)之間的質量比是1/10(v/v)。過濾和在真空下於40℃乾燥48小時之後,沉澱的聚合物以白色粉末形式回收。
藉尺寸排斥層析法定出聚合物的特性。此聚合物以1 g/l溶於經BHT安定的THF中。使用單分散聚苯乙烯標準品進行校正。
-數量平均分子量(Mn):9300 g/mol
-重量平均分子量(Mw):11100 g/mol
-分散性(Mw/Mn):1.19
之後藉由將3.1 g的聚合物引至100 g的聚丙二醇甲醚乙酸酯中,然後在具有50 nm孔隙的Entegris濾器上過濾回收,製得防黏層溶液。
然後藉重量測定法定出固體含量,且必要時藉添加溶劑以調整至3.0%。Example 1
In this example, a release layer (hereinafter referred to as ASL2-presentation) according to the present invention is produced:
• Preparation of hydroxy-functional alkoxyamines (AM-OH, initiator) from commercially available alkoxyamine BlocBuilder ® MA sold by Arkema
The following was introduced into a 1 liter round bottom flask degassed by nitrogen purge:
-226.17 g of BlocBuilder ® MA (1 molar equivalent)
-68.9 g of 2-hydroxyethyl acrylate (1 molar equivalent)
-548 g of isopropanol.
The reaction mixture was refluxed (80 ° C) for 4 hours and then the isopropanol was evaporated under vacuum. This gave 297 g of a hydroxy-functional alkoxyamine (AM-OH initiator) in the form of a very viscous yellow oil.
• Preparation of functionalized polystyrene
260.89 g of toluene, and 600 g of styrene and 20.89 g of AM-OH initiator were introduced into a stainless steel reactor equipped with a mechanical stirrer and jacket.
The reaction mixture was stirred and degassed by passing nitrogen at room temperature for 30 minutes.
The set temperature of the reaction medium was then made 115 ° C (material temperature was 108 ° C). The temperature was maintained at 115 ° C throughout the polymerization until the monomer conversion reached 50%. Samples were taken at regular intervals to determine the polymerization kinetics by gravimetric analysis (determination of anhydrous extracts).
Upon reaching 50% conversion, the reaction medium was cooled to 60 ° C and the solvent and residual monomers were distilled off under vacuum. After evaporation, methyl ethyl ketone was added to the reaction medium in an amount to produce about 25% by mass of the polymer solution.
This polymer solution was then introduced dropwise into a beaker containing a non-solvent (heptane) to cause precipitation of the polymer. The mass ratio between the solvent and the non-solvent (methyl ethyl ketone / heptane) was 1/10 (v/v). After filtration and drying under vacuum at 40 ° C for 48 hours, the precipitated polymer was recovered as a white powder.
The characteristics of the polymer are exemplified by size exclusion chromatography. This polymer was dissolved in BHT stabilized THF at 1 g/l. Calibration was performed using monodisperse polystyrene standards.
- number average molecular weight (Mn): 9300 g/mol
- Weight average molecular weight (Mw): 11100 g/mol
- Dispersibility (Mw/Mn): 1.19
The anti-adhesive layer solution was then prepared by introducing 3.1 g of the polymer into 100 g of polypropylene glycol methyl ether acetate and then filtering and recovering on an Entegris filter having a pore size of 50 nm.
The stipulated solids content is then determined by weight and, if necessary, added to the solvent to adjust to 3.0%.
實例2
此實例中,使用用於至高200 mm直徑的矽晶圓之完全整合的UV奈米壓印微影平台(HERCULES,得自設備製造商EVG)評估防黏層在轉移壓印法中的表現。此設備設計用於高產能製造。奈米印刷模組係基於SmartNILTM
技術。比較性地評估兩個防黏層(ASL)溶液:市售防黏層ASL1-EVG和實例1製備之本發明之用於奈米壓印微影製程的新系列防黏層。
層ASL1-EVG藉離心塗覆於直徑200 mm的矽模板上,之後以市售溶劑(純的氫氟醚)(HFE)清理。此模板接著在加熱板上於120℃加熱幾分鐘。自ARKEMA得到的防黏溶液ASL藉離心澱積。此矽模板之後在200℃退火75秒以確保均勻薄層的化學接枝。之後以溶劑(如,丙二醇單甲醚乙酸酯)沖洗以移除未接枝的鏈。
由於與液體的表面張力可用以預測此層的黏著性,所以通常以表面能量的特徵分析來評估防黏層。使用事先澱積的固定液滴影像,在介於液滴輪廓和表面(基線)之間的截面(接觸的三相點)處測定接觸角度。測定水(H2
O)、二碘甲烷(CH2
I2
)和乙二醇(C2
H6
O2
)的漸近接觸角度。使用OWRK方法,由測得的接觸角度計算表面能量。其結果示於表1。經標準方法處理的模板(ASL1-EVG)得到的表面能量(13 mN/m)最低,然而由本發明之防黏層(ASL2-本發明)得到明顯較高的表面能量(44 mN/m)。由於黏著性通常與表面能量值相關,所以對於防黏處理而言,低表面能量通常較佳。但是,此特徵分析並沒有將能夠生成壓印物的材料之特性列入考量。事實上,當兩個表面接觸時,黏著性涉及物理化學現象。造成黏著性的原因尚不完全清楚,因為它們取決於許多相關因素(靜電學、機械錨定、酸鹼相互作用、相互擴散、共價鍵的產生、潤濕性等)。
因此,將壓印材料列入考量,進行額外的特徵分析以評估ASL。評估ASL所用的壓印材料是EVG開發的丙烯酸系材料(參考:EVG-AS1)。此材料,其為UV-可固化的,能夠以極高解析度再現奈米結構,同時保留足夠的撓性使其得以在壓印中輕微變形且不會損及奈米結構。用以特徵化黏著性的方法係基於“雙重懸臂樑”(DCB)方法,此方法為矽晶圓黏著結合技術中常用的方法。
黏著能量的測定結果示於表1。推估ASL1-EVG的黏著能量(G)大於600 mJ/cm2
,而ASL2-本發明測得低黏著能量(G<200 mJ/cm2
)。這些結果揭示了低表面能量與低黏著性相關聯的共同概念。此外,壓印材料先以液態分佈於經防黏層處理的表面上。因此,壓印材料整體潤濕主表面的能力直接與其表面能量有關。因此,本發明之防黏層所得到之較高的表面能量較佳地促進壓印材料流入模板中。
為了要對防黏層性能進行完整的比較性評估,使用分別經防黏層(ASL1-EVG)和本發明之防黏層(ASL2-本發明)處理的專用200 mm晶圓製造壓印物。模板的設計包括具400×400 µm線(相對於壓印方向垂直和水平導向)的網絡、接觸點和密度範圍為0.1至0.3的支柱。對於每種類型的網絡,在500nm的深度上,臨界尺寸分佈在250nm和幾微米之間。矩陣分佈在10×10mm2
的矩陣上。在直徑為200mm的模板上重複矩陣240次。藉由在Applied Materials (COMPLUS 4T-Darkfield Wafer檢查系統)的專用設備上進行的缺陷測量來評估ASL的性能。通過暗場照明方法(dark-field illumination method)進行檢查。優化該調合物以降低雜訊來源並優化缺陷信號。以最佳化的調合物達到100 nm感度。在製造壓印物的整個過程中對兩個模板進行系統缺陷檢查測量。其結果示於圖5。吾等觀察到,對於二個防黏處理,模板的防黏處理步驟不會明顯響表面缺陷。但是,吾等觀察到相較於標準方法(ASL1-EVG),利用本發明之防黏層(ASL2-本發明)製造壓印物之後,壓印物的缺陷度低得多(低約10倍)。
Example 2
In this example, the fully integrated UV nanoimprint lithography platform (HERCULES, available from the device manufacturer EVG) for tantalum wafers up to 200 mm in diameter was used to evaluate the performance of the release layer in transfer imprinting. This equipment is designed for high capacity manufacturing. Nano printing modules are based on SmartNIL TM technology. Two anti-adhesive layer (ASL) solutions were comparatively evaluated: a commercially available anti-adhesive layer ASL1-EVG and a new series of anti-adhesive layers of the present invention for nanoimprint lithography processes prepared in Example 1.
Layer ASL1-EVG was applied by centrifugation onto a 200 mm diameter crucible template and then cleaned with a commercially available solvent (pure hydrofluoroether) (HFE). This template was then heated on a hot plate at 120 ° C for a few minutes. The anti-adhesive solution ASL obtained from ARKEMA was deposited by centrifugation. This ruthenium template was then annealed at 200 ° C for 75 seconds to ensure uniform chemical grafting of the thin layer. The solvent is then rinsed with a solvent such as propylene glycol monomethyl ether acetate to remove the ungrafted chains.
Since the surface tension with the liquid can be used to predict the adhesion of this layer, the anti-adhesion layer is usually evaluated by characteristic analysis of surface energy. The contact angle is determined at a section (the triple point of contact) between the droplet profile and the surface (baseline) using a previously deposited fixed droplet image. The asymptotic contact angles of water (H 2 O), diiodomethane (CH 2 I 2 ), and ethylene glycol (C 2 H 6 O 2 ) were measured. The surface energy is calculated from the measured contact angle using the OWRK method. The results are shown in Table 1. The template treated by the standard method (ASL1-EVG) gave the lowest surface energy (13 mN/m), whereas the anti-adhesive layer (ASL2-present) of the present invention gave significantly higher surface energy (44 mN/m). Since adhesion is usually related to surface energy values, low surface energy is generally preferred for anti-stick processing. However, this feature analysis does not take into account the properties of the material from which the imprint can be produced. In fact, when two surfaces are in contact, adhesion involves physicochemical phenomena. The causes of adhesion are not fully understood, as they depend on many related factors (electrostatics, mechanical anchoring, acid-base interactions, interdiffusion, covalent bond generation, wettability, etc.).
Therefore, the embossed material is taken into consideration and additional characterization is performed to evaluate the ASL. The imprint material used to evaluate ASL is an acrylic material developed by EVG (Reference: EVG-AS1). This material, which is UV-curable, is capable of reproducing the nanostructure at an extremely high resolution while retaining sufficient flexibility to be slightly deformed in the imprint without damaging the nanostructure. The method used to characterize adhesion is based on the "Double Cantilever Beam" (DCB) method, which is a commonly used method in the 矽 wafer adhesion bonding technique.
The measurement results of the adhesion energy are shown in Table 1. It is estimated that the adhesion energy (G) of ASL1-EVG is greater than 600 mJ/cm 2 , and the low adhesion energy (G < 200 mJ/cm 2 ) measured by ASL2- in the present invention. These results reveal a common concept of low surface energy associated with low adhesion. In addition, the embossed material is first distributed in a liquid state on the surface treated with the release layer. Thus, the ability of the embossed material to wet the major surface as a whole is directly related to its surface energy. Thus, the higher surface energy obtained by the release layer of the present invention preferably promotes the flow of imprinted material into the template.
In order to perform a complete comparative evaluation of the release properties, embossments were made using dedicated 200 mm wafers treated with an anti-adhesive layer (ASL1-EVG) and an anti-adhesive layer of the invention (ASL2-invention). The design of the stencil includes a network of 400 x 400 μm lines (vertical and horizontally oriented relative to the embossing direction), contact points and struts ranging in density from 0.1 to 0.3. For each type of network, the critical dimension is distributed between 250 nm and a few microns at a depth of 500 nm. The matrix is distributed over a matrix of 10 x 10 mm 2 . The matrix was repeated 240 times on a template having a diameter of 200 mm. The performance of the ASL was evaluated by defect measurements made on dedicated equipment of Applied Materials (COMPLUS 4T-Darkfield Wafer Inspection System). The inspection was carried out by a dark-field illumination method. Optimize the blend to reduce noise sources and optimize defect signals. Optimize the blend to achieve a 100 nm sensitivity. Systematic defect inspection measurements were performed on the two templates throughout the manufacture of the imprint. The result is shown in Fig. 5. We observed that for the two anti-adhesive treatments, the anti-adhesive treatment step of the template does not significantly affect surface defects. However, we have observed that the impression of the imprint is much lower (about 10 times lower) after the imprint is made using the anti-adhesion layer (ASL2-invention) of the present invention compared to the standard method (ASL1-EVG). ).
1‧‧‧模板1‧‧‧ template
2‧‧‧防黏層 2‧‧‧Anti-adhesive layer
3‧‧‧壓印物 3‧‧‧imprint
圖1至圖4說明轉移壓印法。Figures 1 through 4 illustrate transfer imprinting.
圖5說明模板之系統缺陷檢查測量的結果。 Figure 5 illustrates the results of a system defect inspection measurement of the template.
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??1762830 | 2017-12-21 | ||
FR1762830 | 2017-12-21 | ||
FR1762830A FR3075800B1 (en) | 2017-12-21 | 2017-12-21 | ANTI-STICK COATS FOR TRANSFER PRINTING PROCESSES |
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TW201932519A true TW201932519A (en) | 2019-08-16 |
TWI696653B TWI696653B (en) | 2020-06-21 |
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TW107145887A TWI696653B (en) | 2017-12-21 | 2018-12-19 | Process for transfer imprinting |
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EP (1) | EP3729194A1 (en) |
JP (1) | JP6997321B2 (en) |
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CN (1) | CN111492308B (en) |
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CN111941714B (en) * | 2020-07-03 | 2022-06-28 | 东莞市天沛塑料有限公司 | EPS plastic foam demolding process |
CN113075858A (en) * | 2021-03-26 | 2021-07-06 | 歌尔股份有限公司 | Method for processing intermediate transfer template |
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US3008920A (en) * | 1959-04-27 | 1961-11-14 | Dow Chemical Co | Method of inhibiting homopolymerization in graft copolymers with copper salts |
US20030080471A1 (en) * | 2001-10-29 | 2003-05-01 | Chou Stephen Y. | Lithographic method for molding pattern with nanoscale features |
US20030071016A1 (en) * | 2001-10-11 | 2003-04-17 | Wu-Sheng Shih | Patterned structure reproduction using nonsticking mold |
FR2866026B1 (en) * | 2004-02-06 | 2008-05-23 | Arkema | RADICAL EMULSION POLYMERIZATION PROCESS USING WATER-SOLUBLE ALCOXYAMINES |
TWI248859B (en) * | 2004-11-24 | 2006-02-11 | Ind Tech Res Inst | Manufacture of mold core used in nanoimprint |
US8011916B2 (en) * | 2005-09-06 | 2011-09-06 | Canon Kabushiki Kaisha | Mold, imprint apparatus, and process for producing structure |
JP2011148117A (en) | 2010-01-19 | 2011-08-04 | Fujifilm Corp | Imprinting mold release agent |
KR20130071426A (en) * | 2010-03-30 | 2013-06-28 | 호야 가부시키가이샤 | Mold having release layer for imprinting, method for producing mold having release layer for imprinting, and method for producing copy mold |
JP5606826B2 (en) | 2010-08-24 | 2014-10-15 | Hoya株式会社 | Release layer for imprint, mold with release layer for imprint, and method for producing mold with release layer for imprint |
JP5459042B2 (en) | 2010-04-23 | 2014-04-02 | 横浜ゴム株式会社 | Manufacturing method of tire manufacturing bladder |
FR2974094A1 (en) | 2011-04-15 | 2012-10-19 | Arkema France | PROCESS FOR PREPARING SURFACES |
FR2983773B1 (en) * | 2011-12-09 | 2014-10-24 | Arkema France | PROCESS FOR PREPARING SURFACES |
KR101820200B1 (en) * | 2012-04-10 | 2018-01-18 | 다이킨 고교 가부시키가이샤 | Resin mold material composition for imprinting |
US10126648B2 (en) * | 2012-05-25 | 2018-11-13 | Micro Resist Technology Gesellschaft Für Chemische Materialien Spezieller Protoresistsysteme Gmbh | Composition suitable for use as a release-optimized material for nanoimprint processes and uses thereof |
JP6283355B2 (en) * | 2013-04-11 | 2018-02-21 | 綜研化学株式会社 | Laminate |
FR3008986B1 (en) * | 2013-07-25 | 2016-12-30 | Arkema France | METHOD OF CONTROLLING THE PERIOD CHARACTERIZING THE MORPHOLOGY OBTAINED FROM A MIXTURE OF BLOCK COPOLYMER AND (CO) POLYMER FROM ONE OF THE BLOCKS |
FR3010414B1 (en) * | 2013-09-09 | 2015-09-25 | Arkema France | PROCESS FOR OBTAINING NANO-STRUCTURED THICK FILMS OBTAINED FROM A BLOCK COPOLYMER COMPOSITION |
FR3014876B1 (en) * | 2013-12-13 | 2017-03-31 | Arkema France | METHOD FOR PRODUCING A BLOCK COPOLYMER FILM ON A SUBSTRATE |
FR3031749B1 (en) * | 2015-01-21 | 2018-09-28 | Arkema France | METHOD FOR ENHANCING THE CRITICAL DIMENSIONAL UNIFORMITY OF ORDINATED BLOCK COPOLYMER FILMS |
FR3031751B1 (en) * | 2015-01-21 | 2018-10-05 | Arkema France | METHOD OF REDUCING DEFECTS IN AN ORDINATED BLOCK COPOLYMER FILM |
KR102536039B1 (en) * | 2016-12-22 | 2023-05-23 | 일루미나, 인코포레이티드 | imprinting device |
CN115717337A (en) * | 2017-04-17 | 2023-02-28 | 康奈尔大学 | Fluorine-free oil-proof coating and manufacturing method and application thereof |
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JP6997321B2 (en) | 2022-01-17 |
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EP3729194A1 (en) | 2020-10-28 |
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TWI696653B (en) | 2020-06-21 |
CN111492308A (en) | 2020-08-04 |
JP2021508169A (en) | 2021-02-25 |
US20240103361A1 (en) | 2024-03-28 |
KR20200093668A (en) | 2020-08-05 |
US11880131B2 (en) | 2024-01-23 |
WO2019122705A1 (en) | 2019-06-27 |
CN111492308B (en) | 2023-10-31 |
KR102446759B1 (en) | 2022-09-22 |
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